New classes of copolymers, poly[oxy( chloromethyl) ethylene]/poly[oxy((alkylthio) methyl) ethylene] copolymers (CE-ATEs), poly[oxy((alkylthio)methyl)ethylene]s (ATEs), poly[ oxy( chloromethyl) ethylene] /poly[oxy(( alkylsulfonyl) methyl)ethylene] copolymers (CE-ASEs), and poly[oxy(( alkylsulfonyl) methyl) ethylene]s (ASEs) have been made for the first time. The thioether-containing polymers (CE-ATEs and ATEs) were synthesized by reacting poly[oxy( chloromethyl) ethylene] (CE, poly( epichlorohydrin)) with different amounts of sodium alkanethiolates. The sulfone-containing polymers (CE-ASEs and ASEs) were synthesized by oxidizing the CE-ATEs and ATEs using m-chloroperoxybenzoic acid. The Fox equation, a linear relationship, fit the T-g/composition data for most CE-ATEs. The T-g＇s of the CE-ASEs showed positive deviations from those calculated using the Fox equation. The Johnston equation, in which steric and/or polar interactions between dissimilar monomeric units are considered by using T-gAB (the T-g of the AB or BA dyad), fit the T-g/composition data for all copolymers in this study.